Triphenylphosphine → 2,3,9,10-Tetrahydro-8H-[1,4]dioxino[2,3-f]chromen-2-ylmethyl 4-methylbenzenesulfonate

HRID 49257

反応式

HRID 49257 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C@@H:13]2[O:18][C:17]3[C:19](CCCO)=[C:20]([O:23][CH2:24][C:25]4C=CC=C[CH:26]=4)[CH:21]=[CH:22][C:16]=3[O:15][CH2:14]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[H][H].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>CO.[Pd]>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][CH:13]2[O:18][C:17]3=[C:19]4[C:20](=[CH:21][CH:22]=[C:16]3[O:15][CH2:14]2)[O:23][CH2:24][CH2:25][CH2:26]4)(=[O:10])=[O:9])=[CH:4][CH:3]=1

参加物

7

反応物 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 86586536[(2R)-7-(benzyloxy)-8-(3-hydroxypropyl)-2,3-dihydro-1,4-benzodioxin-2-yl]methyl 4-methylbenzenesulfonateHCID 178418361HCID 178418361、化合物

生成物 1

HCID 185460132,3,9,10-Tetrahydro-8H-[1,4]dioxino[2,3-f]chromen-2-ylmethyl 4-methylbenzenesulfonate

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 887Methanol溶媒2 回

実験手順

A solution of 2.0 g (4.1 mmole) of [(2R)-7-(benzyloxy)-8-(3-hydroxypropyl)-2,3-dihydro-1,4-benzodioxin-2-yl]methyl 4-methylbenzenesulfonate in 100 mL of methanol was added to a slurry of 0.30 g of 10% palladium on carbon in 30 mL of methanol in 500 mL Parr hydrogenation bottle. The mixture was treated with 50 psi of hydrogen on a Parr shaker for 15 hours. The catalyst was then removed by filtration through celite and the filtrate concentrated in vacuum to 1.6 g of a colorless oil. The oil was dissolved in 100 mL of benzene, 2.1 g (8.0 mmole) of triphenylphosphine and 1.6 g (8.0 mmole) of diisopropylazodicarboxylate added and the mixture stirred at room temperature for 5 days. The solvent was then removed in vacuum and the residue column chromatographed on silica gel with methylene chloride as eluant to give 1.2 g of the (R)-enantiomer of the title compound as a pale yellow oil. 1H-NMR (CDCl3): doublet 7.8 δ (2H); doublet 7.35 δ (2H); doublet 6.6 δ (1H); doublet 6.35 δ (1H); multiplet 4.4 δ (1H); multiplet 4.2 δ (3H); triplet 4.1 (2H); doublet of doublets 4.0 δ (1H); multiplet 2.55 δ (2H); singlet 2.45 δ (3H); multiplet 1.9 δ (2H).

後処理

  1. customThe catalyst was then removed by filtration through celite
  2. concentrationthe filtrate concentrated in vacuum to 1.6 g of a colorless oil
  3. dissolutionThe oil was dissolved in 100 mL of benzene
  4. customThe solvent was then removed in vacuum
  5. customthe residue column chromatographed on silica gel with methylene chloride as eluant

出典と根拠

ORDレコード
ord-74dc9b1d2b28475baa9a3f14393a053d
出典データセット
uspto-grants-2004_03
特許番号
US06706736B2

関連ノート

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